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81.
[reaction: see text] Base-promoted cyclocondensation of C-chloro oximes with cyclic 1,3-diketones affords functionalized isoxazoles in good yield and under convenient reaction conditions. This process enables the synthesis of highly substituted products with notable functional group tolerance. The products obtained are directly converted to a variety of polyketide-derived polycyclic structures including xanthenes, anthracenes, and benzophenones. 相似文献
82.
83.
β-(1-Phenylthio)cyclopropyl enones can be conveniently prepared via reaction of the lithium salts of α-hydroxymethylene ketones with 1-lithio-1-phenylthiocyclopropane and are converted efficiently by treatment with aqueous acid to γ-keto cyclobutanones and less successfully by thermolysis to -γ-keto phenylthiocyclopentenes. 相似文献
84.
Szekeres E Acosta E Sabatini DA Harwell JH 《Journal of colloid and interface science》2005,287(1):273-287
Solubilization of dodecanol-limonene binary oil mixtures has been studied in saturated Winsor type I and III sodium dihexyl sulfosuccinate microemulsions. The systems showed different oil solubilization behavior below and above dodecanol volume fraction 0.2. Below 0.2 dodecanol volume fraction regular Winsor type microemulsions formed. The oil solubilization was characterized in this concentration range by the optimum salinity and the maximum characteristic length. Dodecanol showed Langmuirian-type surface excess adsorption at the vicinity of the surfactant layer. Variation of the optimum salinity and middle phase characteristic length with increasing dodecanol concentration could be linked to changes in the dodecanol surface excess. These relationships were used to develop new mathematical models for the optimum salinity and characteristic length as a function of oil phase composition. Both models yield excellent agreement with the data. Above dodecanol volume fraction 0.2 regular Winsor type III microemulsions are not formed. Therefore our new models are not applicable in this concentration range. 相似文献
85.
The metallochromic reagent chrome azurol S, when used in hexamine buffer at pH 4.9, reacts rapidly with monomeric and small polymeric forms of aluminium(III) in aged hydrolysed solutions. It is unreactive toward the polymer Al13(OH)7+32 and colloidal Al(OH)3 and the hydroxyaluminosilicates, imogolite and allophane. The reagent is appropriate for rapid semi-quantitative analysis of labile aluminium in acid lake waters or acid soils. 相似文献
86.
Yuko Ogata Pamela M. Quizon Nancy S. Nightlinger Pongkwan Sitasuwan Casey Snodgrass L. Andrew Lee Jeffrey D. Meyer Richard S. Rogers 《Rapid communications in mass spectrometry : RCM》2022,36(3):e9222
Rationale
The multi-attribute method (MAM) has become a valuable mass spectrometry (MS)-based tool that can identify and quantify the site-specific product attributes and purity information for biotherapeutics such as monoclonal antibodies (mAbs) and fusion molecules in recent years. As we expand the use of the MAM at various stages of drug development, it is critical to enhance the sample preparation throughput without additional chemical modifications and variability.Methods
In this study, a fully automated MAM sample preparation protocol is presented, where rapid desalting in less than 15 minutes is achieved using miniaturized size-exclusion chromatography columns in pipette tips on an automated liquid handler. The peptide samples were analyzed using an electrospray ionization (ESI) orbitrap mass spectrometer coupled to an ultra-high-performance liquid chromatography (UHPLC) system with a dual column switching system.Results
No significant change was observed in product attributes and their quantities compared with manual, low-artifact sample preparation. The sample recovery using the buffer exchange tips was greatly enhanced over the manual spin cartridges while still demonstrating excellent reproducibility for a wide variety of starting sample concentrations. Unlike a plate desalting system, the individual columns provide flexibility in the number of samples prepared at a time and sample locations within plates.Conclusions
This automated protocol enables the preparation of up to 96 samples with less “at-bench” time than the manual preparation of a smaller batch of samples, thereby greatly facilitating support of process development and the use of the MAM in quality control.87.
Differential expression of the skeletal muscle proteome in mdx mice at different ages 总被引:2,自引:0,他引:2
The mdx mouse is the most commonly used animal model for Duchenne muscular dystrophy (DMD), a disease caused by the absence of dystrophin. Although much has been done to elucidate the structure and function of dystrophin and the dystrophin-associated glycoprotein complex (DGC), little is known about the cascade of molecular events triggered by the absence of dystrophin that lead to muscle degeneration. To study the molecular basis of DMD, we decided to systematically study the skeletal muscle proteome in mdx mice at different ages. By using two-dimensional (2-D) gel electrophoresis, we defined changes in the protein expression pattern between mdx and control muscles. Approximately 46 differentially expressed proteins from the cytosolic fraction of mdx hindlimb muscles at three months of age were detected by 2-D gel analysis, of which 24 were identified by matrix assisted laser desorption/ionization- mass spectrometry. Most of the proteins fell into five groups of functionally related proteins. These functional categories are (i) metabolism and energy production, (ii) serine protease inhibitor family, (iii) growth and differentiation, (iv) calcium homeostasis, and (v) cytoskeletal reorganization and biogenesis. The potential roles of the differentially expressed proteins are discussed in the context of the mdx phenotype. Finally, we analyzed alterations of protein expression in mdx mice at one and six months of age to determine how protein expression changes with disease progression. 相似文献
88.
Cellulase retention and sugar removal by membrane ultrafiltration during lignocellulosic biomass hydrolysis 总被引:1,自引:0,他引:1
Technologies suitable for the separation and reuse of cellulase enzymes during the enzymatic saccharification of pretreated
corn stover are investigated to examine the economic and technical viability of processes that promote cellulase reuse while
removing inhibitory reaction products such as glucose and cellobiose. The simplest and most suitable separation is a filter
with relatively large pores on the order of 20–25 mm that retains residual corn stover solids while passing reaction products
such as glucose and cellobiose to form a sugar stream for a variety of end uses. Such a simple separation is effective because
cellulase remains bound to the residual solids. Ultrafiltration using 50-kDa polyethersulfone membranes to recover cellulase
enzymes in solution was shown not to enhance further the saccharification rate or overall conversion. Instead, it appears
that the necessary cellulase enzymes, including β-glucosidase, are tightly bound to the substrate; when fresh corn stover
is contacted with highly washed residual solids, without the addition of fresh enzymes, glucose is generated at a high rate.
When filtration was applied multiple times, the concentration of inhibitory reaction products such as glucose and cellobiose
was reduced from 70 to 10 g/L. However, an enhanced saccharification performance was not observed, most likely because the
concentration of the inhibitory products remained too high. Further reduction in the product concentration was not investigated,
because it would make the reaction unnecessarily complex and result in a product stream that is much too dilute to be useful.
Finally, an economic analysis shows that reuse of cellulase can reduce glucose production costs, especially when the enzyme
price is high. The most economic performance is shown to occur when the cellulase enzyme is reused and a small amount of fresh
enzyme is added after each separation step to replace lost or deactivated enzyme. 相似文献
89.
Thermal degradation studies of alkyl-imidazolium salts and their application in nanocomposites 总被引:1,自引:0,他引:1
Walid H Awad Jeffrey W Gilman Marc Nyden Thomas E Sutto Paul C Trulove Douglas M Fox 《Thermochimica Acta》2004,409(1):3-11
Increasing the thermal stability of organically-modified layered silicates is one of the key points in the successful technical application of polymer-layered silicate nanocomposites on the industrial scale. To circumvent the detrimental effect of the lower thermal stability of alkyl ammonium-treated montmorillonite, a series of alkyl-imidazolium molten salts were prepared and characterized by elemental analysis, thermogravimetry (TGA) and thermal desorption mass spectroscopy (TDMS). The effect of counter ion, alkyl chain length and structural isomerism on the thermal stability of the imidazolium salts was investigated. Alkyl-imidazolium-treated montmorillonite clays were prepared by ion exchange of the imidazolium salts with Na-montmorillonite. These organically-modified clays were characterized by X-ray diffraction (XRD), TDMS and thermogravimetry coupled with Fourier transform infrared spectroscopy (TGA-FTIR), and compared to the conventional quaternary alkyl ammonium montmorillonite. Results indicate that the counter ion has an effect on the thermal stability of the imidazolium salts, and that imidazolium salts with PF6−, N(SO2CF3)2− and BF4− anions are thermally more stable than the halide salts. A relationship was observed between the chain length of the alkyl group and the thermo-oxidative stability; as the chain length increased from propyl, butyl, decyl, hexadecyl, octadecyl to eicosyl, the stability decreased. The results also show that the imidazolium-treated montmorillonite has greater thermal stability compared to the imidazolium halide. Analysis of the decomposition products by FTIR provides an insight about the decomposition products which are water, carbon dioxide and hydrocarbons. 相似文献
90.
Tilson JL Naleway C Seth M Shepard R Wagner AF Ermler WC 《The Journal of chemical physics》2004,121(12):5661-5675
A valence full configuration interaction study with a polarized double-zeta quality basis set has been carried out for the lowest 49 electronic states of AmCl(+). The calculations use a pseudopotential treatment for the core electrons and incorporate a one-electron spin-orbit interaction operator. Electrons in the valence s, p, d, and f subshells were included in the active space. The resulting electronic potential energy curves are largely repulsive. The chemical bonding is ionic in character with negligible participation of 5f electrons. The molecular f-f spectroscopy of AmCl(+) arises essentially from an in situ Am(2+) core with states slightly redshifted by the presence of chloride ion. Am(+)+Cl asymptotes which give rise to the few attractive potential energy curves can be predicted by analysis of the f-f spectroscopy of isolated Am(+) and Am(2+). The attractive curves have substantial binding energies, on the order of 75-80 kcal/mol, and are noticeably lower than recent indirect measurements on the isovalent EuCl(+). An independent empirical correlation supports the predicted reduction in AmCl(+) binding energy. The energies of the repulsive curves are strongly dependent on the selection of the underlying atomic orbitals while the energies of the attractive curves do not display this sensitivity. The calculations were carried out using our recently developed parallel spin-orbit configuration interaction software. 相似文献